JP2001509819A - Sulfinic acid derivatives and their production and use - Google Patents

Abstract

(57) Abstract The present invention relates to a sulfinic acid compound of the formula (I). Wherein the substituents are as defined in the description. These novel sulfinic acid compounds can be used as reducing agents that do not release formaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION Sulfinic acid derivatives and their production and use   The present invention relates to sulfinic acid derivatives and their production and various fields of application With regard to their use in.   As is known, sulfinic acid H_TwoSO_TwoIs one of the strongest known reducing agents . The free acid is unstable. So its stable and correspondingly manageable guidance Only commercially available in body form.   Today, the following sulfinic acid derivatives have gained commercial importance. 1. Sodium dithionite (fiber bleaching, vat dyeing and weaving in papermaking) Bleaching, mineral bleaching, reduction of heavy metals in industrial wastewater) 2. Sodium formaldehyde sulfoxylate dihydrate (fiber color print, Redox cocatalyst in textile bleaching, emulsion polymerization, heavy metal reduction, pharmaceuticals) 3. Formamidine sulfinic acid (fiber bleaching and textile bleaching in papermaking) 4. Zinc formaldehyde sulfoxylate (textile printing and textile bleaching)   All of the sulfinic acid derivatives mentioned above are used in the form of aqueous solutions or dispersions. You. In aqueous media, dithionite and alkali metal formamidine sulfite Phosphate-free formamidine sulfinic acid is substantially insoluble in water and In acid form it has very little reducing action-is only stable for a short time. as a result Even at room temperature, they have excellent reducing capacity and excellent bleaching on fibers Show the effect. Sodium formaldehyde sulfoxylate and formaldehyde Aqueous preparations of zinc dosulfoxylate are stable at room temperature for several months. As a result, this Both formaldehyde sulfoxylates have their true conversion at temperatures above 90 ° C. Shows the original effect. In strongly alkaline or strongly acidic media or in the presence of suitable strong oxidizing agents In the presence of both formaldehyde sulfoxylates, of course, below 90 ° C. Has a reducing effect at temperature.   This particular property of formaldehyde sulfoxylate, ie, 5 ° C to 9 ° C Produces a very uniform and easily controllable reducing effect at a temperature of 0 ° C Conducting makes it usable for free radical initiated emulsion polymerization. In this case, Mualdehyde sulfoxylate is used in various emulsion polymerization systems. SBS In the case of cold production of lenbutadiene rubber), polymerization is initiated using organic peroxides. You. At a polymerization temperature as low as about 5 ° C., the organic peroxide is converted to the necessary free radicals. Does not decompose. Peroxide cleavage must be initiated by a catalytic amount of iron (II) salt Absent. Iron in oxidation stage 2 is converted to oxidation stage 3 and is no longer suitable for peroxide cleavage And With the help of formaldehyde sulfoxylate, iron (III) ions Reduced to iron (II) ions, peroxide cleavage and free radical initiation continue . In other emulsion polymerization systems, peroxides such as hydrogen peroxide or peroxodisulfate Oxidizing compounds are used as free radical formers. Free radical formation rate The reducing agent is again used to increase the pressure. An example that can be mentioned is Holmardich Dosulfoxylate, bisulfite, ascorbic acid, isoascorbic acid and Sodium Eri It is a slobate. Formaldehyde sulfoxylate, especially formaldehyde Sodium sulfoxylate is a particularly effective and good value reducing agent. Has been proven. However, during the reduction process, formaldehyde sulfo Xylic acid releases formaldehyde. Must not contain formaldehyde Plastic or polymer dispersions may be sulfite, ascorbic acid, isoasco Polymerized using rubic acid or sodium erythrobate. Holmualde Since the non-hydrating reducing agent is a weaker reducing agent, formaldehyde sulfoxylic acid The disadvantages of a more incomplete polymerization compared to the salts must be tolerated. More ass Use of corbic acid, isoascorbic acid and sodium erythrobate Leads to undesired yellowing of the mer.   The purpose of the present invention is that their chemistry is to formaldehyde sulfoxylate. As similar as possible, but not releasing formaldehyde during or after use A novel sulfinic acid derivative.   Surprisingly, this purpose is now a type of sulfite that will be described in more detail later. It has been found that this can be achieved by acid derivatives.   Therefore, the present invention provides a compound of formula (I): And a salt thereof.   Where:   M represents a hydrogen atom, an ammonium ion, a monovalent metal ion, or a periodic table I a, IIa, IIb, IVa or VIIIb equivalent of a divalent metal ion;   R¹Is OH or NR^FourR^FiveWhere R^FourAnd R^FiveIs independently H or C₁-C₆-Is alkyl;   R^TwoIs H, alkyl, alkenyl, cycloalkyl or aryl (these Is based on C₁-C₆-Alkyl, OH, OC₁-C₆Alkyl, halogen and C F_ThreeMay have 1, 2 or 3 substituents independently selected from ) R;   R^ThreeIs COOM, SO_ThreeM, COR^Four, CONR^FourR^FiveOr COOR^Four(M, R^Four And R^FiveIs the same as above. ) Or if R^TwoIs unsubstituted or If the substituted aryl is^ThreeIs also H.   For the purposes of the present invention, the following expressions have the following meanings:   Alkyl is preferably straight-chain or 1-6 carbon atoms, in particular 1-4 carbon atoms. Represents a branched alkyl. Examples of alkyl groups are methyl, ethyl, n-propyl, i-propyl. Isopropyl, n-butyl, t-butyl, n-hexyl and the like.   The same applies to the alkyl groups in the O-alkyl.   Alkenyl is preferably straight-chain or has 3 to 8, especially 3 to 6, carbon atoms. Or a branched alkenyl group. Preferably, the alkenyl group is an allyl group.   Cycloalkyl groups are in particular C_Three-C₆-Cycloalkyl, cyclopentyl And cyclohexyl are particularly preferred.   Aryl (also aryl in aralkyl) is preferably phenyl Or naphthyl. If the aryl group is a phenyl group and is substituted If it has, it preferably has two substituents. They are especially second and / or Or in fourth place.   Halogen represents F, Cl, Br and I, preferably Cl and Br.   M is preferably an ammonium ion, an alkali metal ion, or an alkali It is the equivalent of earth metal ion or zinc ion. Preferred alkali metal ions are Especially sodium and potassium ions. Preferred alkaline earth metal ions are Particularly magnesium and calcium ions.   R¹Is preferably a hydroxyl or amino group.   R^TwoIs preferably a hydrogen atom or an alkyl which may be substituted as described above. Or aryl. It is preferably one or two hydroxyl and And / or have an alkoxy substituent.   R^ThreeIs preferably COOM or COOR^Four(M and R^FourIs the same as above. )so If or if R^TwoIs aryl which may be substituted as described above. If so, it may be a hydrogen atom.   Preferred specific examples are those wherein, in the formula (I), M is an alkali metal ion or an alkali metal ion. The equivalent of earth metal ion or zinc ion, R¹Is hydroxyl or A amino group;^TwoIs H or alkyl;^ThreeIs COOM or COOR^Four (M is the equivalent of H, an alkali metal ion, or an alkaline earth metal ion, R^FourIs C₁-C₆-Alkyl. ).   Another preferred embodiment is a compound of formula (I)   M is an alkali metal ion, an alkaline earth metal ion or zinc The equivalent of an ion, R¹Is a hydroxyl or amino group;^TwoIs unsubstituted Reel or aryl substituted as above, especially hydroxyphenyl or C₁ -C_Four-Alkoxyphenyl, R_ThreeCovers compounds where is a hydrogen atom You.   These new compounds are prepared from dithionite. Advantageously sulfinic acid Salts having desirable cations are also used for the compounds. Corresponding to dithionite By reacting with an aromatic aldehyde,^TwoIs unsubstituted or substituted ally R^ThreeIs a hydrogen atom. This reaction is an example Using sodium dithionate and 2-hydroxybenzaldehyde, the following reaction This can be illustrated by an equation. All other compounds of formula (I) have the dithionites corresponding to the corresponding 1,2-dicarbo. The compound is produced by reacting with a carbonyl compound or its sulfonic acid equivalent. The 1,2-dicarbonyl compounds used are in particular glyoxylic acid or the corresponding Keto compounds and their esters. This reaction is sodium dithionite Using glyoxylic acid and can be illustrated by the following reaction scheme:   The reaction is generally performed in an aqueous medium in the presence of a base. The aqueous medium is methanol, Water-soluble organic solvents such as ethanol and isopropanol can be included. Use Bases which can be used are, in particular, alkali metal hydroxides and alkaline earth metal hydroxides. You. The reaction is generally performed at ambient temperature and is exothermic, so heating the reaction mixture Not generally needed. The desired product generally precipitates from the reaction mixture or is Add polar water-soluble organic solvents such as tanol, isopropanol and acetone Thus, precipitation can occur. The resulting product is in the form of a salt, which if desired If so, it can be converted to the free acid by acidification or treatment with an acidic ion exchanger. Can be.   Furthermore, the products are generally prepared in a mixture with the corresponding metal sulphite. many In this case, the mixture contains the corresponding sulfonic acid and water of crystallization. New compound Are entrained components in the usual manner, for example by recrystallization from water or aqueous ethanol. Can be separated from   For practical use, it is not necessary to separate the entrained components. Conversely, new The action of the reference compound is enhanced by these companion components. Therefore, the present invention refers to To provide a mixture with the ingredients. For this purpose, up to 40% of metal sulphite salts And amounts of up to 60% sulfonic acid may be present. The water content may be up to 30%.   These new compounds are comparable in reducing action to formaldehyde sulfoxylate Is a reducing agent. However, they can be used before, during or after use. It has the advantage of not discharging aldehyde. Therefore, the new compound is a formaldehyde It is preferentially used in areas where generation is undesirable. For example, they are textile stamps Printing, especially color removal Printing, fabric bleaching or vat dyeing as a reducing agent, or minerals such as kaolin Used as a reducing agent for the bleaching of materials and fibers, for example cellulose fibers Can be. However, they allow the polymerization to be carried out at It is preferably used as a cocatalyst in emulsion polymerization together with a product initiator. This purpose Therefore, if desired, Fe²⁺, Mn²⁺Along with oxidizable metal ions such as Ruphinic acid can be used. Then these metal ions are oxidized by sulfin Counter ion of the compound, ie, M = Fe²⁺, Mn²⁺Is advantageously used as etc. You.   For use, the novel compounds are generally used with conventional additives and auxiliaries . In this regard, there are no particular restrictions, except that reducing compounds must not be used. No.   The following examples illustrate the invention without limitation. Purity numbers given in the examples Relates to products containing water of crystallization to be produced. In other words, purity depends on the water content of crystallization. Significantly higher when taken into account. Example 1   2-hydroxyphenylhydroxymethylsulfinic acid sodium salt,   50 ml of 2-hydroxybenzaldehyde and 50% strength hydroxide 45 g of an aqueous thorium solution is mixed with commercially available sodium hydrosulfite (sodium dithionite). )) To 90 g of the aqueous solution. After the exothermic reaction is completed, the resulting crude product is And recrystallized from a methanol / ethanol / water mixture . 2-hydroxyphenylhydroxymethylsulfinic acid sodium salt having a purity of 7 Manufactured with 5.8%. Sulfinic acid content is determined using iodometric titration Was. IR spectral data (T = transmittance) are as follows. Example 2   4-methoxyphenylhydroxymethylsulfinic acid sodium salt:   63 g of 4-methoxybenzaldehyde and 50% strength aqueous sodium hydroxide solution 45 g was added to a commercially available aqueous sodium hydrosulfite solution 90. Steaming the resulting solution The precipitation precipitated the crude product. This sulphy Acid sodium salt is purified by recrystallization from methanol / ethanol / water mixture 68%. Corresponding sulfonic acid sodium salt present as second component did. Example 3   2-Hydroxy-2-sulfinate acetate sodium salt:   358 g of commercially available sodium hydrosulfite in 800 ml of water and 50% The reaction between 268 g of xylic acid and 285 g of a 50% strength sodium hydroxide solution is carried out in 2-hydroxy. Doxy-2-sulfinate disodium acetate was provided in a 95% yield. solid Contained 43% sulfinic acid (without hydrated water). methanol Crystallization from water / ethanol / water mixture shows good crystallization of hydrate of sulfinic acid Gave. Sulfur-containing components were determined using iodine titration. This sulfin The acid shows a reaction with indanthrene paper at about 75 ° C.   The IR spectrum shows the following peak. ¹³C nuclear magnetic resonance spectrum (63 MHz):   δ (ppm): 93.8 (s); 177.7 (s) Example 4   Zinc 2-hydroxy-2-sulfinate acetate:   Reaction of 33 g of zinc dust with sulfur dioxide in an aqueous medium gave zinc dithionite. This was reacted in situ with 136 g of 50% strength glyoxylic acid. End of exothermic reaction Thereafter, 75 g of ZnO was added. The crude product present in the filtrate is precipitated using methanol. Settled. From 20% sulfinic acid and 48% sulfonic acid (determined by iodometric titration) Had become. Example 5   Disodium 2-hydroxy-2-sulfinate propionate:   Starting from 89 g of commercial sodium hydrosulfite in water, 40 g of pyruvate, A crude product was obtained by reaction with about 78 g of a 50% strength sodium hydroxide solution. Coarse The product contains 40% sulfinic acid and is a methanol / ethanol / water mixture And recrystallized. The content was determined by iodometric titration. Corresponding sulfonic acid dinatto The lithium salt was present as a second component. The measured IR spectral signals are as follows: there were. Example 6   Ethyl 2-hydroxy-2-sulfinate propionate sodium salt:   90 g of commercially available sodium hydrosulfite in an aqueous solution was mixed with 60 g of ethyl pyruvate; After reacting with 39 g of 50% strength sodium hydroxide, 2-hydroxy-2-sulphur Ethyl finatopropionate sodium salt precipitates during the exothermic reaction as a hydrate did. The separated, dried crude product contains 79% of sulfinic acid (calculated without water of crystallization). I was out. This content was determined by iodometric titration. The IR spectral signal is as follows Can be summarized. Example 7   For paste printing on black cloth, a printing paste having the following formula was selected. Base formula for printing paste: 434 g of water Potassium carbonate 100g KL100 thickener (carboxymethyl starch) 6g Lame Blind IND8 (guar ether + starch ether) 40g Glycerol 14gPrint Gen (self-emulsifying mineral oil) 6g Base prescription 600g   The formaldehyde-free reducing agent corresponding to Example 3 or e.g. Sodium formaldehyde sulfoxylate was then added to this base formulation.Mixture 1 Comparative mixture Base prescription 600g Base prescription 600g 2-formaldehyde sulfo corresponding to Example 3 Sodium hydroxy-2-sulfoxylate 107 g of sodium disodium acetate 213g salt (crude product)   The resulting mixture was then applied one after another to a black cloth and dried in a drying cabinet . The fabric was then aged at 102 ° C. for 10 minutes, during which time the dye was reduced. chic Thoroughly cleaned cloth and remover pre-applied to remove toner and other chemicals The bleached fabric at the location became clear.   It is clear that the colorless printing was performed well. What kind of preparation washing Did not provide any sort of problem. Dinato 2-hydroxy-2-sulfinate acetic acid Lium salts can thus be used for textile color printing according to the state of the art. You. The results of this colorless printing are summarized in Table 1. Example 8Kaolin bleaching   The starting concentration of kaolin was 250 g / l. The slurry has a pH of 6.5 Was. After homogenizing the kaolin suspension using a stirrer for 30 minutes, the pH was reduced to half. It was adjusted to 2.5 using concentrated sulfuric acid. 2-hydroxy-2-s corresponding to Example 3 Rufinoacetic acid disodium salt or sodium formaldehyde sulfoxylate Was added as a 10% strength solution and was based on the solids content of the kaolin suspension (See Table 2). Reaction conditions:   Temperature: room temperature   pH: 2.5   Reaction time: 2 hours  Preparation containing 2-hydroxy-2-sulfinate acetate disodium salt Gives good results in bleaching kaolin. Hydroxyacetylsulfinic acid The preparation containing the disodium salt is sodium formaldehyde sulfoxylate Responded 3-4 times faster than the system. Bleaching of minerals, especially kaolin, is currently in bleaching It is possible according to the technology. Example 9 (comparative example)   400 g of water, Airvol 205 (polyvinyl alcohol, 88% hydrolysis , Degree of polymerization = 500; Air Products and Chemicals , Inc. 286 g of a 10% aqueous solution of Airvol 107 (polyvinyl alcohol) Alcohol, 98% hydrolysis, degree of polymerization = 500, Air Products and d Chenicals, Inc. 286 g of a 10% solution of   CO-887 (a nonionic surfactant, Rhone-Poulenc, Inc. 47% aqueous solution of Igepal containing about 30 moles of ethylene oxide) g into a 3.8 liter pressurized reactor, 4.8% aqueous 1% iron (II) sulfate solution. g. The reaction mixture was adjusted to pH 3. using 1.75 g of a 50% strength phosphoric acid solution. Adjusted to 3. Next, 1710 g of vinyl acetate monomer was weighed and added. Reaction mixing The material was stirred at 900 rpm and heated to 35 ° C. Next, 200 g of ethylene gas Introduced at pressures up to 0.4 atm. next,   270 g of water   30 g of isoascorbic acid   0.8 g of 29% concentration ammonium hydroxide 10% strength aqueous solution of isoascorbic acid having the following composition (pH = 4) Was added.   The polymerization has a composition of 589 g of deionized water and 11.1 g of 35% hydrogen peroxide. Starting with a total of 10 g of a 0.65% strength aqueous hydrogen peroxide solution.   After the initiation of the polymerization, the remaining ammonium isoascorbate / isoascorbic acid solution The remaining 295.1 g was weighed in during 4 hours. 0.65% hydrogen peroxide solution The remaining 590.1 g was the reaction mixture warming from 35 ° C. to 55 ° C. over 1 hour. And control the polymerization so that the reaction mixture is then maintained at 55 ° C. for 3 hours. Was added to After a total polymerization time of 4 hours, the free vinyl acetate monomer The content was still 1.5%.   Cool the reaction mixture to 35 ° C and transfer to a pressureless vessel to degas excess ethylene. did. The free acetic acid monomer remaining in the emulsion is then Polymerization was performed by adding 20 g of a scorbic acid aqueous solution and 3.5% hydrogen peroxide. As a result, the free vinyl acetate monomer was reduced to a final content of 0.5% or less. polymer The pH of the emulsion was adjusted to the desired pH (Table 3 using 14% aqueous ammonia). (See below). Table 3 shows the physical properties of the polymer emulsion (latex). Summarized. Example 10 (comparative example)   The emulsion polymerization was repeated as in Example 9 and the isoascorbic acid Instead of monium / isoascorbic acid, 270 g of water and formaldehyde An aqueous solution consisting of 22.1 g of sodium rufoxylate was used. The results are shown in Table 3. About. Example 11 (cocatalyst in emulsion polymerization)   The emulsion polymerization was repeated as in Example 9 and the isoascorbic acid 33 g of the reducing agent of Example 3 (crude product) instead of monium / isoascorbic acid And an aqueous solution consisting of 270 g of water. The results are summarized in Table 3. Example 12Groundwood pulp bleaching Conditions for groundwood pulp bleaching: Stock concentration: 5.4% Bleaching temperature: 75 ° C Bleach additive: bleach 0.2 / 0.4 / 0.6 / 0.8 / 1.0%,             Absolutely dry (dry weight) Bleaching time: 30 minutes   For bleaching, 100 g of groundwood pulp were weighed in each case into polyethylene bags. Aqueous solutions were prepared for the addition of bleach (1 ml of each solution was bleached to 0%). . 2%). After pipetting the bleach solution, immediately tie the bag and close the contents. Mix thoroughly by kneading the bag. Bleaching temperature is thermostat (water Bath).   After the required bleaching time, transfer the pulp slurry to a measuring flask and measure the pH after bleaching. Specified. Next, the volume was adjusted to 300 ml with tap water, and the pulp slurry was stirred. Thus, the mixture was homogenized. Use a conventional suction system A sheet was formed using a sheet filmer. The resulting sheet is converted to a sheet former In a vacuum for 12 minutes. Whiteness R457 of all formed sheets is whiteness Determined using a measuring device (Elepho 2000 from Datacolor). Conclusion The results are summarized in Table 4.Example 13Deinked pulp bleaching Conditions for deinking pulp bleaching: Stock concentration: 7.4% Bleaching temperature: 75 ° C Bleach additive: bleach 0.2 / 0.4 / 0.6 / 0.8 / 1.0%,             Absolutely dry (dry weight) Bleaching time: 60 minutes   70 g of deinked pulp were weighed in each case into polyethylene bags for bleaching . Aqueous solutions were prepared for the addition of bleach (1 ml of these solutions contained 0.1 ml of each bleach. 2%). After pipetting the bleach, immediately squeeze the bag and close the contents Mix thoroughly by kneading the bag. Bleaching temperature is thermostat (water bath ).   After the required bleaching time, transfer the pulp slurry to a measuring flask and measure the pH after bleaching. Specified. Next, the volume was adjusted to 300 ml with tap water, and the pulp slurry was stirred. Thus, the mixture was homogenized. Use a conventional suction system A sheet was formed using a sheet filmer. The resulting sheet is converted to a sheet former In a vacuum for 15 minutes. Whiteness R457 of all formed sheets is whiteness Determined using a measuring device (Elepho 2000 from Datacolor). Conclusion The results are summarized in Table 5.

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Claims (1)

[Claims]   1. Formula (I): Sulfinic acid compounds and salts thereof: Where:   M is a hydrogen atom, an ammonium ion, a monovalent metal ion, or the periodic table Ia , IIa, IIb, IVa or VIIIb equivalent of a divalent metal ion:   R¹Is OH or NR^FourR^FiveWhere R^FourAnd R^FiveIs independently H or C₁ -C₆-Is alkyl;   R^TwoIs H, alkyl, alkenyl, cycloalkyl or aryl (these The group is C₁-C₆-Alkyl, OH, OC₁-C₆-Alkyl, halogen and CF_Three May have 1, 2 or 3 substituents independently selected from ) ;   R^ThreeIs COOM, SO_ThreeM, COR^Four, CONR^FourR^FiveOr COOR^Four(M, R^Four And R^FiveIs the same as above. ) Or if R^TwoIs unsubstituted or as described above Is a highly substituted aryl, R^ThreeIs also H.   2. In the formula (I), whether M is ammonium or an alkali metal ion Or the equivalent of an alkaline earth metal ion or a zinc ion. Ruphinic acid compounds.   3. In the formula (I), R¹Is OH or NH_TwoThe sulf of claim 1 or 2, wherein Diacid compounds.   4. In the formula (I), R^TwoIs a hydrogen atom, or one or two hydrides Alkyl or aryl which can have a roxyl or alkoxy substituent The sulfinic acid compound according to claim 1, which is a sulfur group.   5. In the formula (I), R^ThreeIs COOM or COOR^FourWhere M and R^Four Is the same as defined above.   6. In the formula (I),   M is an alkali metal ion, or an alkaline earth metal ion or a zinc ion Is the equivalent of   R¹Is OH or NH_TwoAnd   R^TwoIs H or alkyl;   R^ThreeIs COOM or COOR^FourWherein M is as defined above and R^FourH Or C₁-C₆-Alkyl The sulfinic acid compound according to claim 1, which is   7. In the formula (I), R^TwoIs one or two hydroxyl or alcohol Aryl which can have a xy substituent;^ThreeIs H. Finic acid compounds.   8. In the formula (I), R^TwoIs hydroxyphenyl or C₁-C_Four-Alkoxy The sulfinic acid compound according to claim 7, which is phenyl.   9. In the formula (I),   M is an alkali metal ion or an alkaline earth metal ion or a zinc ion Equivalent,   R¹Is OH or NH_TwoAnd   R^TwoIs hydroxyphenyl or C₁-C_Four-An alkoxyphenyl,   R^ThreeIs a hydrogen atom The sulfinic acid compound according to claim 1, which is   10. Compounds of the following formula (M = Na, K, Mg, Ca, Zn):  11. The sulfinic acid compound according to any one of claims 1 to 10, and the sulfinic acid A sulfonic acid or a salt thereof corresponding to the acid compound, and a corresponding sulfite. Mixtures that do or do not contain.   12. The mixture of claim 11 having the following composition:   20 to 90% by weight of a compound of formula (I)   Sulfonic acid corresponding to the compound of formula (I) 0-60% by weight   M_TwoSO_Three                                  0-40% by weight   13. 13. The mixture of claim 12, having the following composition:   61-98% by weight of 2-hydroxyphenylhydroxymethyl   Sulfinic acid sodium salt   2-hydroxyphenylhydroxymethyl 2 to 15% by weight   Sulfonic acid sodium salt   Sodium sulfite 0-37% by weight   14． 13. The mixture of claim 12, having the following composition:   4-methoxyphenylhydroxymethyl 60-98% by weight   Sulfinic acid sodium salt   4-methoxyphenylhydroxymethyl 2 to 15% by weight   Sulfonic acid sodium salt   Sodium sulfite 0-38% by weight   15. 13. The mixture of claim 12, having the following composition:   2-hydroxy-2-sulfinate 40-73% by weight   Disodium acetate   2-hydroxy-2-sulfonate acetic acid 2-7% by weight   Disodium salt   Sodium sulfite 0-33% by weight   Water 5-30% by weight   16. 13. The mixture of claim 12, having the following composition:   2-hydroxy-2-sulfinate 20-70% by weight   Zinc acetate   2-hydroxy-2-sulfonate acetic acid 5 to 60% by weight   Zinc salt   Water 5-30% by weight   17． 13. The mixture of claim 12, having the following composition:   2-hydroxy-2-sulfinate 38-70% by weight   Propionic acid disodium salt   2-hydroxy-2-sulfonate 5 to 30% by weight   Propionic acid disodium salt   Sodium sulfite 0-33% by weight   Water 5-30% by weight   18. 13. The mixture of claim 12, having the following composition:   2-hydroxy-2-sulfinate 60-80% by weight   Ethyl propionate sodium salt   2-hydroxy-2-sulfonate 0-5% by weight   Ethyl propionate sodium salt   Sodium sulfite 0-5% by weight   5-20% by weight of water   19. 11. Conventional additives and auxiliaries and the sulphate according to claim 1 At least one of the diacid compounds or the mixture of claims 11 to 18; A composition comprising at least one.   20. 11. The reduction of the sulfinic acid compound according to any one of claims 1 to 10. Use as base agent.   21. As a cocatalyst in emulsion polymerization or as a redo in plastics production Use of claim 20 as a catalyst catalyst system.   22. As a reducing agent in textile printing, textile bleaching or vat dyeing, or 21. Use according to claim 20 as a reducing bleach for mineral refining or fiber finishing.